This invention relates to polytrimethylene ether esters, and their manufacture and use.
Polytrimethylene ether glycol (xe2x80x9cPO3Gxe2x80x9d) and its use in thermoplastic elastomers, as well as in other applications, have been described in a number of patents and patent applications. PO3G can be prepared by dehydration of 1,3-propanediol or by ring opening polymerization of oxetane. PO3G can also be prepared from 1,3-propanediol, preferably as described in U.S. Published patent application Ser. Nos. 2002/7043 A1 and 2002/10374 A1, both of which are incorporated herein by reference.
Polyether ester elastomer comprising polytrimethylene ether ester soft segment and tetramethylene and trimethylene ester hard segments are described in U.S. patent application Ser. Nos. 10/016,195 and 10/016,023 both of which are incorporated herein by reference. Polytrimethylene ether ester amides are described in U.S. patent application Ser. No. 10/073,745, filed Feb. 11, 2002, which is incorporated herein by reference. Polyurethanes and polyurethane ureas are described in U.S. patent application Ser. No. 10/215,575, filed Aug. 9, 2002, which is incorporated herein by reference.
While not wishing to be bound by theory, it is believed that, due to the incompatibility of the hard and the soft segments, phase separation occurs. The two phases constitute the elastomeric matrix. The hard segments form microdomains of crystallites, while the soft segments and a fraction of the crystallizable hard component that has not reached crystalline order form the amorphous phase. It is known to those skilled in the art that the better the distinction between the crystalline microdomain and the amorphous phases the better the elastic properties. Phase separation and microdomain formation in block polymers directly influence thermal behavior, dynamic mechanical properties, mechanical and rheological properties, and permeability and transport phenomena of the elastomeric system. It is taught that the morphology of the elastomeric system, and its properties, depend heavily on the crystallization conditions of both the hard and soft segments. The block that crystallizes first has a tendency to xe2x80x9cfreezexe2x80x9d the entire structure, and in this way, to impose the crystallization of the other block. Thus, in order to form a clear two phase morphology, the more amorphous in nature of the soft segment, the better, as it will take longer and more difficult to crystallize (either by itself or induced by the hard segment residues in the soft segment phase).
In U.S. patent application Ser. Nos. 10/016,195 and 10/016,023, it was taught that a slower crystallizing polytrimethylene ether glycol soft segment in the block polymer elastomer provides better elastic properties (e.g., unloaded power, stress decay, % set) as compared to that of polytetramethylene ether glycol soft segment. Thus the soft segment needs to be as amorphous as possible, as measured by the crystallization rate. While polytrimethylene ether glycol itself provides an excellent soft segment, even more amorphous and more slowly crystallizing soft segments are desirable. More amorphous soft segments would lead to a better two-phase morphology and give further improvements in the final thermoplastic elastomers.
There is a continuing need to improve polytrimethylene ether glycol and thermoplastic elastomers made therefrom. The present invention provides a novel random polytrimethylene ether ester and novel thermoplastic elastomers with advantageous properties.
The invention is directed to a random polytrimethylene ether ester prepared by polycondensation of 1,3-propanediol reactant and about 10 to about 0.1 mole % of aliphatic or aromatic diacid or diester.
It is also directed to a random polytrimethylene ether ester by polycondensation of about 90 to about 99.9 mole % of 1,3-propanediol reactant, calculated based on the amount of 1,3-propanediol and 1,3-propanediol units, and about 10 to about 0.1 mole % of aliphatic or aromatic diacid or diester.
In another embodiment, it is directed to a random polytrimethylene ether ester by polycondensation of about 80 to about 99.1 mole % of 1,3-propanediol reactant, calculated based on the amount of 1,3-propanediol and 1,3-propanediol units, about 10 to about 0.1 mole % of aliphatic or aromatic diacid or diester, and up to about 10 mole % of diol reactant other than 1,3-propanediol reactant, calculated based on the amount of diol and diol units.
In a further embodiment, it is directed to a random polytrimethylene ether ester by polycondensation of 1,3-propanediol reactant and about 10 to about 0.1 mole % of aliphatic or aromatic diacid.
The random polytrimethylene ether ester is preferably prepared from about 90 to about 99.9 mole % of the 1,3-propanediol reactant and the about 10 to about 0.1 mole % of aliphatic or aromatic diacid. In another embodiment, it is preferably prepared from about 80 to about 99.9 mole % of the 1,3-propanediol reactant, the about 10 to about 0.1 mole % of aliphatic or aromatic diacid, and up to about 10 mole % of diol reactant other than 1,3-propanediol reactant.
Preferably the 1,3-propanediol reactant is selected from the group consisting of 1,3-propanediol, and oligomers and prepolymers of 1,3-propanediol having a degree of polymerization of 2 to 9, and mixtures thereof.
In one preferred embodiment, the random polytrimethylene ether ester of claim 1 wherein the 1,3-propanediol reactant is 1,3-propanediol. In another preferred embodiment, the 1,3-propanediol reactant is selected from the group consisting of prepolymers of 1,3-propanediol having a degree of polymerization of 2 to 9 and mixtures thereof.
Preferably the aliphatic or aromatic diacid or ester is selected from the group consisting of aromatic dicarboxylic acids and esters, and combinations thereof.
Preferred is the aliphatic or aromatic diacid, and preferably the diacid is selected from the group consisting of aromatic dicarboxylic acids and combinations thereof. Preferably the aliphatic or aromatic diacid is an aromatic diacid selected from the group consisting of terephthalic acid, isophthalic acid, bibenzoic acid, naphthalic acid, bis(p-carboxyphenyl)methane, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 4,4xe2x80x2-sulfonyl dibenzoic acid, p-(hydroxyethoxy)benzoic acid, and combinations thereof.
Preferably the aliphatic or aromatic diacid or diester is selected from the group consisting of terephthalic, bibenzoic, isophthalic and naphthalic acid; dimethyl terephthalate, bibenzoate, isophthlate, naphthalate and phthalate; and combinations thereof.
Preferably the aromatic diacid is selected from the group consisting of terephthalic acid and isophthalic acid. Most preferred it is terephthalic acid.
Preferably the random polytrimethylene ether ester is prepared from about 95 to 99.5 mole %, more preferably about 97.5 to 99 mole %, of the 1,3-propanediol reactant and about 5 to about 0.5 mole %, more preferably about 2.5 to about 1 mole %, of the aliphatic or aromatic diacid.
In another embodiment, the random polytrimethylene ether ester is preferably prepared from about 85 to about 99.5 mole %, more preferably about 87.5 to about 99 mole %, of the 1,3-propanediol reactant, about 5 to about 0.5 mole %, more preferably about 2.5 to about 1 mole %, of aliphatic or aromatic diacid or diester, and up to about 10 mole % of diol other than 1,3-propanediol reactant.
In one preferred embodiment, the random polytrimethylene ether ester is prepared by a process comprising the steps of: (a) providing (1) 1,3-propanediol reactant, (2) aliphatic or aromatic acid or ester; and (3) polycondensation catalyst; and (b) polycondensing the 1,3-propanediol reactant to form a random polytrimethylene ether ester, preferably at less than one atmosphere pressure.
In another preferred embodiment, the random polytrimethylene ether ester is prepared by a process continuous process comprising: (a) continuously providing (i) 1,3-propanediol reactant, (ii) aliphatic or aromatic acid or ester and (iii) polycondensation catalyst; and (b) continuously polycondensing the (i) 1,3-propanediol reactant and (ii) aliphatic or aromatic acid or ester to form random polytrimethylene ether ester.
The invention is also directed to thermoplastic elastomers prepared from the random polytrimethylene ether ester as a soft segment and a hard segment polymer selected from the group consisting of polyesters, polyamides, polyurethane, and polyurethane urea. One preferred embodiment is directed to a polyether ester elastomer comprising a soft segment from the random polytrimethylene ether ester and alkylene ester hard segment, preferably a C2 to C12 alkylene ester hard segment, preferably tetramethylene ester hard segment or trimethylene ester hard segment. Another preferred embodiment is directed to a polytrimethylene ether ester amide comprising a soft segment from the random polytrimethylene ether ester of claim 1 and a polyamide hard segment. Yet a further preferred embodiment is directed to a polyurethane or polyurethane urea elastomer prepared from (a) the random polytrimethylene ether ester, (b) diisocyanate and (c) diol or diamine chain extender.
The introduction of the minor amount terephthalic acid provides advantages, including: (a) decreasing the time for the reaction to produce desired molecular weight; and (b) providing a means to further decrease the crystallization rate and thereby providing a more amorphous character in the soft segments in the thermoplastic elastomers made with the polytrimethylene ether ester, as compared with those made with polytrimethylene ether glycol. Other advantages are described below.
The invention is directed to random polytrimethylene ether esters prepared from 1,3-propanediol reactant and about 10 to about 0.1 mole % of aliphatic or aromatic diacid or diester, and their manufacture and use.
By xe2x80x9c1,3-propanediol reactantxe2x80x9d is meant 1,3-propanediol, and oligomers and prepolymers of 1,3-propanediol having a degree of polymerization of 2 to 20, preferably 2 to 9, and mixtures thereof. In addition, xe2x80x9coligomerxe2x80x9d is used to refer to dimer and trimer of 1,3-propanediol; xe2x80x9cprepolymerxe2x80x9d is used to refer to 1,3-propanediol based compounds having a degree of polymerization of 4 to 20, and xe2x80x9cpolytrimethylene ether glycolxe2x80x9d and xe2x80x9cpolytrimethylene ether esterxe2x80x9d are used to refer to polymers having a Mn of 500 or more. The preferred starting material for this invention is 1,3-propanediol and, for simplicity, applicants will refer to 1,3-propanediol in describing the invention.
Diols other than 1,3-propanediol, and oligomers and prepolymers from such diols, can be used in preparing the invention, and are collectively referred to as xe2x80x9cdiol reactantsxe2x80x9d herein. The random polytrimethylene ether ester can contain up to about 10 mole % of repeating units from such diol reactants, calculated based on the amount of diol and diol units in the diol reactant. Suitable diols include aliphatic diols, for example 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 3,3,4,4,5,5-hexafluro-1,5-pentanediol, 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-hexadecafluoro-1,12-dodecanediol, cycloaliphatic diols, for example 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and isosorbide, and polyhydroxy compounds, for example glycerol, trimethylolpropane, and pentaerythritol. Preferred diols are selected from the group consisting of 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-ethyl-2-(hydroxymethyl)-1,3-propanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, isosorbide, and mixtures thereof. In one preferred embodiment, such repeat units are not present in the polytrimethylene ether ester.
The aliphatic or aromatic diacid or diester can be aliphatic (including cycloaliphatic) or aromatic, or a combination thereof, and is preferably selected from the group consisting of aromatic dicarboxylic acids and esters (preferably short chain alkyl esters, and more preferably methyl esters), and combinations thereof. Preferred are aliphatic or aromatic diacids, and most preferred are aromatic dicarboxylic acids and combinations thereof.
Preferably the aliphatic or aromatic diacid is an aromatic diacid selected from the group consisting of terephthalic acid, isophthalic acid, bibenzoic acid, naphthalic acid, bis(p-carboxyphenyl)methane, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 4,4xe2x80x2-sulfonyl dibenzoic acid, p-(hydroxyethoxy)benzoic acid, and combinations thereof. Of these, terephthalic acid and isophthalic acid, and mixtures thereof are preferred, with terephthalic acid being most preferred.
Preferably the aliphatic or aromatic diester is selected from the group consisting of dimethyl terephthalate, bibenzoate, isophthlate, naphthalate and phthalate; and combinations thereof. Of these, dimethyl terephthalate and isophthalate, and mixtures thereof are preferred, with dimethyl terephthalate being most preferred.
Most preferred is terephthalic acid.
The polytrimethylene ether ester has a number average molecular weight (Mn) of at least about 500, more preferably at least about 1,000, even more preferably at least about 1,500 and most preferably in the order of 2,000. The Mn is preferably up to about 3,000, and more preferably up to about 2,500. Reference herein to molecular weight, unless otherwise indicated is to Mn.
The random polytrimethylene ether esters of the invention are polytrimethylene ethers that predominately comprise polyether residues with a minor proportion of polyester linkages distributed randomly throughout the polymer. In particular, this invention relates to the manufacture of polymers of 1,3-propanediol containing a minor amount of terephthalic acid, with said terephthalic acid groups widely separated along the polymer chain. The terephthalic acid ester units are distributed along a predominantly polytrimethylene ether polymer backbone, and preferably do not contain two consecutive trimethylene terephthalate groups, i.e., are substantially, and preferably entirely, free of the monomer sequence (terephthalate)-1,3-propylene-(terephthalate).
The properties of the polytrimethylene ether esters of the invention are similar to those of polytrimethylene ether glycols. For example, the melting point of a polytrimethylene ether ester of the invention is a few degrees lower (e.g., 4 to 7xc2x0 C.) than the melting point of a comparable polytrimethylene ether glycol, while the Tg is up to about 20xc2x0 C. higher than a comparable a polytrimethylene ether glycol. This increase in Tg correlates to the terephthalic acid content.
The random polytrimethylene ether esters of the invention are prepared by polycondensation (including (a) esterification or transesterification and (b) etherification) of 1,3-propanediol and terephthalic acid. The polytrimethylene ether esters are made using a mole ratio of from 0.1 to 10 mole %, preferably at least 0.5 mole %, most preferably at least 1 mole %, and preferably up to 5 mole %, most preferably up to 2.5 mole %, of diacid or diester. Above 10 mole % significant formation of the repeat ester sequences occurs (e.g. the monomer sequence (terephthalate)-1,3-propylene-(terephthalate) occurs). The formation of this sequence has the effect of (a) reducing the flexibility of the polyol chain and therefore reducing its effectiveness as a soft segment.
The process can be batch, semi-continuous, continuous, etc., and the acid or diester can be added prior to or during the reaction. The polytrimethylene ether esters of the invention are preferably prepared using the methods described in U.S. Published patent application Ser. Nos. 2002/7043 A1 and 2002/10374 A1, both of which are incorporated herein by reference, with further reaction of the diacid or diester to the 1,3-propanediol reactant. Thus, in one preferred embodiment, the random polytrimethylene ether ester is prepared by a process comprising the steps of: (a) providing (1) 1,3-propanediol reactant, (2) aliphatic or aromatic acid or ester; and (3) polycondensation catalyst; and (b) polycondensing the 1,3-propanediol reactant to form a random polytrimethylene ether ester, preferably at less than one atmosphere pressure. In one preferred embodiment thereof, the process comprises the steps of: (a) providing (1) 1,3-propanediol and (2) a polycondensation catalyst; (b) condensing 1,3-propanediol to form oligomer or prepolymer of 1,3-propanediol having a degree of polymerization of 2 to 20, preferably 2 to 9, or a mixture comprising one or more thereof; and (c) polycondensing the oligomer or prepolymer or mixture to form a polytrimethylene ether ester at less than one atmosphere pressure. The aliphatic or aromatic acid or ester can be added any time prior to or during step (b), or prior to step (c), or both. Preferably step b) is carried out at about atmospheric pressure, the pressure in step c) is less than 300 mm Hg (40 kPa), the temperature in step b) is about 150 to about 210xc2x0 C. and the temperature in step c) is about 150 to about 250xc2x0 C.
The polytrimethylene ether esters of the present invention can be produced continuously using the procedure of U.S. Published patent application Ser. No. 2002/10374 A1, preferably by adding the diacid or diester sequentially at the polymerization stage whereat the glycol has reached the desired molecular weight, and before the hydrolysis step. Thus, in another preferred process, the random polytrimethylene ether ester is prepared by a process continuous process comprising: (a) continuously providing (i) 1,3-propanediol reactant, (ii) aliphatic or aromatic acid or ester and (iii) polycondensation catalyst; and (b) continuously polycondensing the (i) 1,3-propanediol reactant and (ii) aliphatic or aromatic acid or ester to form random polytrimethylene ether ester. Preferably the polycondensing is carried out in two or more reaction stages. Preferably the polycondensing is carried out at a temperature greater than about 150xc2x0 C., more preferably greater than about 180xc2x0 C. and preferably less than about 250xc2x0 C., more preferably less than about 210xc2x0 C. Preferably the polycondensation is carried out at a pressure of less than one atmosphere, preferably at least about 50 mm Hg. In one preferred continuous process the polycondensation is carried out in an up-flow co-current column reactor and the 1,3-propanediol reactant and polytrimethylene ether glycol flow upward co-currently with the flow of gases and vapors, preferably where the reactor has 3 to 30 stages, more preferably 8 to 15 stages. The 1,3-propanediol reactant can be fed to the reactor at one or multiple locations. In another preferred embodiment, the polycondensation is carried out in a counter current vertical reactor wherein the 1,3-propanediol reactant and polytrimethylene ether glycol flow in a manner counter-current to the flow of gases and vapors. Preferably the reactor has two or more stages. Preferably the 1,3-propanediol reactant is fed at the top of the reactor, and preferably the 1,3-propanediol reactant is also fed at multiple locations to the reactor. In yet another preferred embodiment, the polycondensation is first carried out in at least one prepolymerizer reactor and then continued in a column reactor, the 1,3-propanediol reactant comprises 90 weight % or more 1,3-propanediol, and in the prepolymerizer reactor the 1,3-propanediol is polymerized with the catalyst to a degree of polymerization of at least 5. Most preferably, in the at least one prepolymerizer reactor the 1,3-propanediol is polymerized with the catalyst to a degree of polymerization of at least 10 and the column reactor comprises 3 to 30 stages. Preferably the at least one prepolymerizer reactor is a well-mixed tank reactor. The diacid or diester can be fed at one or more places, and is preferably fed in the earlier stages of the columns, for example anywhere in the first ⅔rds of the stages (e.g., stages 1 to 10 of a 15-stage reactor).
The polycondensation catalysts preferred for these reactions are described in U.S. Published patent application Ser. Nos. 2002/7043 A1 and 2002/10374 A1, both of which are incorporated herein by reference. They include homogeneous catalysts such as Lewis Acids, Bronsted Acids, super acids, and mixtures thereof. Examples include inorganic acids, organic sulfonic acids, heteropolyacids, and metal salts thereof. Preferred are sulfuric acid, fluorosulfonic acid, phosphorus acid, p-toluenesulfonic acid, benzenesulfonic acid, phosphotungstic acid, phosphomolybdic acid, trifluoromethanesulfonic acid, 1,1,2,2-tetrafluoroethanesulfonic acid, 1,1,1,2,3,3-hexafluoropropanesulfonic acid, bismuth triflate, yttrium triflate, ytterbium triflate, neodymium triflate, lanthanum triflate, scandium triflate and zirconium triflate. Heterogeneous catalysts, such as zeolites, fluorinated alumina, acid-treated silica, acid-treated silica-alumina, heteropolyacids and heteropolyacids supported on zirconia, titania, alumina and/or silica, can also be used. Preferred are the aforementioned homogeneous catalysts, and most preferred is sulfuric acid.
The diacid or diester addition leads to faster polymerization kinetics (i.e., faster reaction time) and results in a higher molecular weight polymer (i.e., random polytrimethylene ether ester) formed in the same reaction time as compared to a comparable polymerization carried out with 1,3-propanediol alone.
Purification (batch or continuous, etc.) can be carried out by hydrolysis as described in U.S. Published patent application Ser. Nos. 2002/7043 A1 and 2002/10374 A1, both of which are incorporated herein by reference, or by other means. The molecular weight of the polytrimethylene ether esters of the invention is not reduced during the hydrolysis step, indicating the 1,3-propylene-terephthalate ester linkage in the backbone of the polytrimethylene ether esters of the invention remains intact.
The conventional additives commonly used in polyether esters, polyether glycols and thermoplastic elastomers can be incorporated into the 1,3-propanediol reactants, the polytrimethylene ether esters, and the thermoplastic elastomers and other products made from the polytrimethylene ether esters, by known techniques. Such additives include delusterants (e.g., TiO2, zinc sulfide or zinc oxide), colorants (e.g., dyes), stabilizers (e.g., antioxidants, ultraviolet light stabilizers, heat stabilizers, etc.), fillers, flame retardants, pigments, antimicrobial agents, antistatic agents, optical brighteners, extenders, processing aids, viscosity boosters, and other functional additives. As a specific example, an antioxidant prevents polyethers are subject to oxidation during storage. A preferred antioxidant stabilizer is 2,6 di-tert-butyl-p-cresol, also known as butylated hydroxy toluene or BHT, used at a level of 50 to 500 micrograms/g based on the weight of the polymer. The most preferred level is 100 micrograms/g.
The polytrimethylene ether esters can be used in the same manner as polytrimethylene ether glycol.
The invention is also directed to thermoplastic elastomer prepared from the random polytrimethylene ether ester as a soft segment and a hard segment polymer selected from the group consisting of polyether esters, polyamides, polyurethanes and polyurethane ureas, which can be prepared and used as described in U.S. patent application Ser. Nos. 10/016,195, 10/016,023, 10/073,745 and 10/016,195, 10/016,023, 10/073,745 and 10/215,575, which are incorporated herein by reference.
In one embodiment, the invention is directed to polyether ester elastomers comprising polytrimethylene ether ester soft segments and alkylene ester hard segments. These are block polymers. They preferably contain C2 to C12 alkylene ester hard segments. Preferred are tetramethylene ester hard segment, such as described in U.S. patent application Ser. No. 10/016,195 and trimethylene ester hard segment, such as described in U.S. patent application Ser. No. U.S. patent application Ser. No. 10/016,023, both of which are incorporated herein by reference. The preferred polyether ester elastomers, as well as their preparation and use, is basically the same as described in U.S. patent application Ser. Nos. 10/016,195 and 10/016,023.
The polyether ester elastomer preferably comprises about 90 to about 60 weight % polytrimethylene ether ester soft segment and about 10 to about 40 weight % alkylene ester hard segment. They preferably contain at least about 70 weight %, more preferably at least about 74 weight %, polytrimethylene ether ester soft segment, and preferably contain up to about 85, more preferably up to about 82 weight %, polytrimethylene ether ester soft segment. They preferably contain at least about 15 weight %, more preferably at least about 18 weight %, and preferably contain up to about 30 weight %, more preferably up to about 26 weight %, alkylene ester hard segment.
The mole ratio of hard segment to soft segment is preferably at least about 2.0, more preferably at least about 2.5, and is preferably up to about 4.5, more preferably up to about 4.0.
The polyether ester is preferably prepared by providing and reacting (a) polytrimethylene ether ester, (b) diol, preferably 1,4-butanediol or 1,3-propanediol, and (c) dicarboxylic acid, ester, acid chloride or acid anhydride. Preferably, the dicarboxylic acid, ester, acid chloride or acid anhydride is an aromatic dicarboxylic acid or ester, more preferably selected from the group consisting of dimethyl terephthalate, bibenzoate, isophthlate, phthalate and naphthalate; terephthalic, bibenzoic, isophthalic, phthalic and naphthalic acid; and mixtures thereof. Most preferred are terephthalic acid and dimethyl terephthalate.
The invention is also directed to fibers prepared from the polyether ester. Preferred fibers include monocomponent filament, staple fiber, multicomponent fiber such as bicomponent fiber (containing the polyether ester as at least one component). The fibers are used to prepare woven, knit and nonwoven fabric.
The polyether esters of this invention can be used to prepare melt spinnable thermoplastic elastomers having excellent strength and stretch-recovery properties.
In another embodiment, the invention is directed to polytrimethylene ether ester amides, similar to those described in U.S. patent application Ser. No. 10/073,745, filed Feb. 11, 2002, which is incorporated herein by reference, and their manufacture and use. These are block polymers. They contain polytrimethylene ether ester soft segments and polyamide hard segments.
The polyamide segment preferably has an average molar mass of at least about 300, more preferably at least about 400. Its average molar mass is preferably up to about 5,000, more preferably up to about 4,000 and most preferably up to about 3,000.
The polytrimethylene ether ester amide preferably comprises 1 up to an average of up to about 60 polyalkylene ether ester amide repeat units. Preferably it averages at least about 5, more preferably at least about 6, polyalkylene ether ester amide repeat units. Preferably it averages up to about 30, more preferably up to about 25, polyalkylene ether ester amide repeat units.
The weight percent of polyamide segment, also sometimes referred to as hard segment, is preferably at least about 10% and most preferably at least about 15% and is preferably up to about 60%, more preferably up to about 40%, and most preferably up to about 30%. The weight percent of polytrimethylene ether ester segment, also sometimes referred to as soft segment, is preferably up to about 90%, more preferably up to about 85%, and is preferably at least about 40%, more preferably at least about 60% and most preferably at least about 70%.
The polytrimethylene ether ester amide comprises polyamide hard segments joined by ester linkages to polytrimethylene ether ester soft segments and is prepared by reacting carboxyl terminated polyamide or diacid anhydride, diacid chloride or diester acid equivalents thereof and polyether ether ester under conditions such that ester linkages are formed. Preferably it is prepared by reacting carboxyl terminated polyamide and polyether ester comprising at least 50 weight %, more preferably at least 75 weight %, and most preferably about 85 to 100 weight %, polytrimethylene ether ester.
In one preferred embodiment the carboxyl terminated polyamide is the polycondensation product of lactam, amino-acid or a combination thereof with dicarboxylic acid. Preferably, the carboxyl terminated polyamide is the polycondensation product of C4-C14 lactam with C4-C14 dicarboxylic acid. More preferably, the carboxyl terminated polyamide is the polycondensation product of lactam selected from the group consisting of lauryl lactam, caprolactam and undecanolactam, and mixtures thereof, with dicarboxylic acid selected from the group consisting of succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, terephthalic acid, and isophthalic acid, and mixtures thereof. Alternatively, the carboxyl terminated polyamide is the polycondensation product of amino-acid with dicarboxylic acid, preferably C4-C14 amino-acid and preferably C4-C14 dicarboxylic acid. More preferably, the carboxyl terminated polyamide is the polycondensation product of amino-acid selected from the group consisting of 11-amino-undecanoic acid and 12-aminododecanoic acid, and mixtures thereof, with dicarboxylic acid selected from the group consisting of succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, terephthalic acid, and isophthalic acid, and mixtures thereof.
In another preferred embodiment, the carboxyl terminated polyamide is the condensation product of a dicarboxylic acid and diamine. Preferably, the carboxyl terminated polyamide is the condensation product of a C4-C14 alkyl dicarboxylic acid and C4-C14 diamine. More preferably, the polyamide is selected from the group consisting of nylon 6-6, 6-9, 6-10, 6-12 and 9-6.
The invention is also directed to shaped articles comprising the polytrimethylene ether ester amide. Preferred shaped articles include fibers, fabrics and films.
Polyurethanes and polyurethane ureas such as those described in U.S. patent application Ser. No. 10/215,575, filed Aug. 9, 2002 can be prepared with the random polytrimethylene ether esters of the invention, and can be used as described therein.
The introduction of the minor amount terephthalic acid provides a means to further decrease the crystallization rate in end products in which polytrimethylene ether esters are incorporated. Thus, thermoplastic elastomers prepared with the random polytrimethylene ether esters of this invention have substantially slower crystallization rates and, as a result, more amorphous character in the soft segments, than comparable thermoplastic elastomers prepared with comparable polytrimethylene ether glycols. For example, polytrimethylene ether glycol having an Mn of 1210 has a crystallization half time of 5.75 minutes at 35xc2x0 C., whereas a comparable random polytrimethylene ether esters of the invention containing 1 mole % of terephthalic acid (equivalent to 2% by weight) has a crystallization half time of 16.13 minutes at 35xc2x0 C. The crystallization half time of the random polytrimethylene ether esters of the invention versus polytrimethylene ether glycol is higher, which results in a slower crystallization of the polyether chains. Therefore, the polytrimethylene ether esters of the invention will stay in an amorphous state longer as compared to homogeneous polyethers such as polytrimethylene ether glycol. This remains true when the polytrimethylene ether esters of the invention is used as soft segment in the thermoplastic elastomers. This propensity for staying in the amorphous state longer results in a better phase separation of the hard and soft segments, which, in turn provides better elastic recovery properties in the thermoplastic elastomers.
The polymers of the present invention are also useful in other applications as similar known polymeric polyethers, such as polytetramethylene ether glycol and polytrimethylene ether glycol. For example, they may be used as one of the starting materials in the manufacture of shaped articles by injection molding, blow molding, extrusion and compression molding, and reactive extrusion in the manufacture of coatings, laminates and adhesives, in the manufacture of packaging and industrial films, and in the manufacture of foams and cast elastomers.